CN106824191A - Application of the bimetallic catalyst in hydrogenolysis of glycerin prepares 1,3- propane diols - Google Patents
Application of the bimetallic catalyst in hydrogenolysis of glycerin prepares 1,3- propane diols Download PDFInfo
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- CN106824191A CN106824191A CN201510882004.1A CN201510882004A CN106824191A CN 106824191 A CN106824191 A CN 106824191A CN 201510882004 A CN201510882004 A CN 201510882004A CN 106824191 A CN106824191 A CN 106824191A
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 235000011187 glycerol Nutrition 0.000 title claims abstract description 30
- 238000007327 hydrogenolysis reaction Methods 0.000 title claims abstract description 24
- 229920000166 polytrimethylene carbonate Polymers 0.000 title description 16
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical class OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 title description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 6
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 230000009467 reduction Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229910015711 MoOx Inorganic materials 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 6
- 229910003091 WCl6 Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Chinese gallotannin Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000005470 impregnation Methods 0.000 abstract description 5
- 238000001354 calcination Methods 0.000 abstract description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 abstract description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- BRARRAHGNDUELT-UHFFFAOYSA-N 3-hydroxypicolinic acid Chemical compound OC(=O)C1=NC=CC=C1O BRARRAHGNDUELT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- -1 glycol ester Chemical class 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- LGUKXHPIRLIAGC-UHFFFAOYSA-N propane-1,3-diol;propane-1,2,3-triol Chemical class OCCCO.OCC(O)CO LGUKXHPIRLIAGC-UHFFFAOYSA-N 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- CFQPVBJOKYSPKG-UHFFFAOYSA-N 1,3-dimethylimidazol-2-one Chemical class CN1C=CN(C)C1=O CFQPVBJOKYSPKG-UHFFFAOYSA-N 0.000 description 1
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- CMDGQTVYVAKDNA-UHFFFAOYSA-N propane-1,2,3-triol;hydrate Chemical compound O.OCC(O)CO CMDGQTVYVAKDNA-UHFFFAOYSA-N 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Abstract
The patent is related to application of the bimetallic catalyst in hydrogenolysis of glycerin prepares 1,3-PD, and a kind of hydrogenolysis of glycerin prepares catalyst of 1,3-PD and preparation method thereof, and catalyst is by WOxCarrier loaded active component molybdenum oxide and platinum are constituted.The preparation method of catalyst includes：A) solvent-thermal method prepares catalyst carrier WOx；B) with the precursor solution incipient impregnation WO of platinumxThen it is vacuum dried and reduces, obtains Pt/WOx；C) by obtained Pt/WOxIncipient impregnation metamolybdic acid ammonium salt solution obtains final catalyst MoO after drying, calcining reduction againx-Pt/WOx.Catalyst obtained by the patent, hydrogenolysis generates 1,3-PD with high selectivity with a temperature of in certain Hydrogen Vapor Pressure can to make glycerine water solution.
Description
Technical field
The present invention relates to the catalyst that a kind of hydrogenolysis of glycerin prepares 1,3-PD, specially WOx
Carrier loaded active component molybdenum oxide and platinum.
The invention is related to the preparation method and applications of above-mentioned catalyst, specially using solvent heat
Method prepares WOx, active component platinum and molybdenum are supported using two step infusion processes, and investigate not
The activity in hydrogenolysis of glycerin prepares 1,3- propane diols and selection with the catalyst under preparation condition
Property.
Technical background
With developing rapidly for biodiesel, the by-product glycerin in production biodiesel process is big
Amount is superfluous, and glycerine converting prepares high value chemicals turns into lifting Biodiesel economy
Effective means.Glycerine can generate 1,3-PD, 1,2-PD etc. by hydrogenolysis,
Wherein 1,3- propane diols is the important monomer for producing PTT (PTT).
PTT is a kind of new type polyester fiber with biodegradability, and it overcomes poly- terephthaldehyde
Sour glycol ester (PET) too hard and polybutylene terephthalate (PBT) (PBT) is too soft to be lacked
Point, while have excellent resilience, chromatophilia, biological degradability etc., thus carpet,
The industries such as Textile Engineering plastics have huge development potentiality.The industry of current 1,3- propane diols is raw
Product method has the oxirane carbonyl hydrogenation method and Degussa and Dupont of Shell companies
The acrolein hydration hydrogenation method of company.
Oxirane carbonyl hydrogenation method (Chinese patent CN1201407A) uses oxirane
3-HPA is generated with synthesis gas under cobalt-base catalyst, then by 3-HPA and hydrogen
The method of 1,3- propane diols is hydrogenated under hydrogenation catalyst effect.Acrolein hydration method (in
State patent CN93114516.3) it is dehydrated under solid acid catalyst using gaseous state glycerine hydrate
Generation methacrylaldehyde, the methacrylaldehyde of generation is hydrated generation 3- hydroxyls third under acidic catalyst effect
Aldehyde, the 3-HPA of generation under conventional hydrogenation catalyst Hydrogenation for 1,3-PD, together
When by-product 1,2- propane diols.
Above-mentioned industrial manufacture process is complicated, and environmental pollution is serious, and gained 1,3-PD contains
Impurity, needs further purified treatment.
Document (Appl.Microbiol.Biotechnol.1992,36,592-597) reports one
The method that 1,3-PD is prepared using Clostridiurn strain bio conversions is planted, can be in 29h
The glycerite conversion of 110g/l is obtained into the 1,3- propane diols of 56g/l afterwards, the method is subject to biology
The influence of metabolic activities, low production efficiency, and because production concentration is low, purifies and separates
Energy consumption needed for 1,3- propane diols is also very high.
Document (Catal.Commun.2008,9,1360-1363) reports one kind in 1,3- bis-
Methyl -2- imidazolones are under solvent, hydrogenolysis of glycerin prepares the method for 1,3-PD, the method
The yield of 1,3- propane diols is 24%.
The Tomishige seminars of Japan report the Rh/SiO of Re modifications2And Ir/SiO2Urge
Agent, author is in Ir-Re/SiO2Fluid sulphuric acid (H is added under catalyst action+/ Re=1), hydrogen
Gas initial pressure 8MPa, at 120 DEG C of reaction temperature, 36 is reacted in 20% glycerine water solution
After h, the high income of 1,3-PD up to 38.0% has been obtained.Subsequent literature (Journal of
Molecular Catalysis A:Chemical.2014,388,177-187) the 3rd is also reported to help
Agent especially Ru it is prepared by hydrogenolysis of glycerin 1,3- propane diols facilitation it is most obvious.
The Jinho Oh of South Korea report the ZrO that Pt is supported on sulfuric acid acidifying2On, with DMI
It is reaction medium, is 7.3MPa in initial hydrogen pressure, 24h is reacted at 170 DEG C of reaction temperature
The high income of 1,3- propane diols up to 55.6% is obtained.
Organic solvent is employed in above-mentioned reaction as reaction medium, and the annex solution for being used
The method of body acid, does not meet the requirement of Green Chemistry.
The direct hydrogenolysis of glycerine prepares 1,3-PD and has obtained very big concern in recent years, because its work
Skill is simple, and raw material is cheap.Document (Chin.J.Catal.2012,33:Although 1257-1261) reporting
A kind of simple mesoporous WO of Pt/3The catalyst of hydrogenolysis of glycerin 1,3-PD is directly used in,
But the overall yield of 1,3- propane diols is still relatively low.So far, document (ChemSusChem
2013,6,1345-1347) it is 100% and the performance of selectivity up to 66% to report conversion ratio
Optimal Pt/WOx/ AlOOH catalyst systems.But it is converted into unit noble metal catalyst unit
For the 1,3-PD yield that time obtains, reduced levels are still in.Also there is text simultaneously
Offer (Journal of Molecular Catalysis A:Chemical.2015,398,391-398) report
Road WOxTo Pt/Al2O3Facilitation.Document (Chem.Lett.2012,41,1720-
- 1722) AlO is reportedxTo Pt Nanoparticles/WO3In hydrogenolysis of glycerin 1,3- propane diols
Facilitation.Even author has also investigated MoOxTo Pt Nanoparticles/WO3Promotion
Effect, unfortunately, in this document, MoOxAddition on the contrary show whole catalyst
Any activity is not gone out.The facilitation and WO of possible auxiliary agentxStructure and the dispersiveness of Pt have
Substantial connection.Whole catalyst system and catalyzing is made a general survey of, current study hotspot is concentrated mainly on Pt/W/Al2O3
System simultaneously develops towards auxiliary agent addition direction.Either improve the pattern of each species, content is still
Crystalline structure sets auxiliary agent species, there is the raising of different degrees of 1,3-PD yield, reacts
Solvent is also generally fixed to the water phase condition of environmental protection, but is all also maintained at pressure higher substantially
(5MPa is in the majority, highest 8MPa) and temperature (180-200 DEG C) higher.In order that glycerine
Direct hydrogenolysis prepares that 1,3-PD reaction condition is gentleer, and yield is further improved, it is necessary to
New catalyst system and catalyzing is further developed on the basis of existing.
The content of the invention
The present invention provides the catalyst and its system that a kind of direct hydrogenolysis of glycerine prepares 1,3- propane diols
Preparation Method, compared with prior art, the inventive technique effectively reduces reaction condition and improves
The selectivity of 1,3-PD, reduces the generation of 1,2-PD.
Patent of the present invention provides the catalyst that a kind of hydrogenolysis of glycerin prepares 1,3-PD, catalyst
Carrier is the WO of hydro-thermal method synthesisx, active component is MoOxAnd platinum.Active component MoOx
0.001%-10% and 0.01%-10% are respectively with the mass content of Pt.
The carrier WO of catalyst of the present inventionxPreparation method be：
By 3 grams of WCl6It is dissolved in 100mL absolute ethyl alcohols, treats WCl6By Huang after being completely dissolved
Color clear solution is transferred in the water heating kettle with liner, by this water heating kettle preheated
36h are placed in 160 DEG C of baking ovens, room temperature is then naturally cooled to, after suction filtration with absolute ethyl alcohol and
Deionized water successively washing for several times, be then placed in 50 DEG C of vacuum drying chambers it is dry carrier
WOx。
MoO is prepared using step impregnation methodx-Pt/WOxCatalyst.Platinum acid chloride solution is used first
Dipping WOxSupported carrier active component Pt, after being vacuum dried 6-12 hours at 50 DEG C, in
Reduced 0.5-5 hours at 100~600 DEG C, Pt/WO is obtainedxCatalyst.Then by Pt/WOx
Catalyst is added in metamolybdic acid ammonium salt solution, and 6-12 hours, Ran Houyu are dried under the conditions of 120 DEG C
Calcining reduction 0.5-5 hours at 100~600 DEG C, final catalyst MoO is obtainedx-Pt/WOx。
Catalyst be applied to glycerine water solution hydrogenolysis prepare 1,3-PD reaction in, reaction condition
It is as follows：Reaction is carried out in batch (-type) tank reactor, and glycerine water solution mass concentration is
1-100%, reaction temperature is 100~300 DEG C, and preferably 120~180 DEG C, Hydrogen Vapor Pressure is
0.1-10MPa, preferably 0.5~7MPa, glycerine are that 0.5-50 is small with the catalyst reaction time
When, preferably 6-24 hours.
The present invention compared with prior art, can significantly improve hydrogenolysis of glycerin and prepare 1,3-PD
Selectivity, improve glycerol conversion yield, effectively suppress 1,2-PD generation.
Specific embodiment
Embodiment 1
The catalyst for using is WOxCarrier loaded active component MoOxAnd platinum.Catalyst
It is Pt%=2% to constitute, MoOx%=0.1%, remaining is WOxCarrier.WOxCarrier is used
Prepared by solvent-thermal method, specific preparation process includes：
A) by 3 grams of WCl6It is dissolved in 100mL absolute ethyl alcohols, treats WCl6After being completely dissolved
Yellow transparent solution is transferred to rapidly in the water heating kettle with liner, this water heating kettle is in preheating
36h is placed in 160 DEG C of good baking ovens, room temperature is then naturally cooled to, with absolute ethyl alcohol and gone
Ionized water successively washing for several times, be then placed in 50 DEG C of vacuum drying chambers it is dry carrier WOx,
2.5<X<3。
B) by platinum acid chloride solution incipient impregnation to WOxOn carrier, room temperature is dried in the shade, Pt's
Loading is 2%, after 50 DEG C of baking ovens vacuum drying 6h, Hydrogen activation, and activation condition is
300 DEG C, Hydrogen Vapor Pressure is 0.1MPa, and hydrogen gas space velocity is 3600h-1, soak time is 1h,
Then by obtained 2%Pt/WOxIncipient impregnation metamolybdic acid ammonium salt solution, MoO againxReason
0.1% is set to by loading.From batch reactor, glycerine water solution mass concentration is
5% (the common 12g of solution), catalytic amount is that (catalyst is 1 with qualities of glycerin ratio to 0.3g:2), react
Temperature is 140 DEG C, and reaction pressure is 1MPa, and the reaction time is 12h.
Embodiment 2
Change MoOxLoad capacity be 0.05%, other conditions are same as Example 1.
Embodiment 3
Change MoOxLoad capacity be 0.2%, other conditions are same as Example 1.
Comparative example 1
Without MoOx2%Pt/WOxCatalyst, other conditions are same as Example 1.
Embodiment 1~3 and the direct hydrogenolysis of the glycerine water solution of comparative example 1 prepare 1,3- propane diols and are listed in
Table 1, contrasts, MoO according to embodiment 1 and 2,3xOptimal loading be 0.1%.Implement
Example 1 be free of MoOxCOMPARATIVE CATALYST understand, the component MoO of load regulation twoxCatalysis afterwards
Agent shows very excellent choosing in the reaction that glycerine selection hydrogenolysis prepares 1,3- propane diols
Selecting property and conversion ratio higher.It is contemplated that explanation MoOxTo the load with solvent structure
Body and the Pt/WO for impregnatingxCatalyst has facilitation, is conducive to improving hydrogenolysis of glycerin preparation 1,3-
Propane diols selectivity.
The hydrogenolysis of glycerin of table 1 prepares the catalytic performance contrast of 1,3- propane diols
* other include a small amount of methane, ethane, propane, methyl alcohol, ethanol, ethylene glycol, overall conservation of matter.
Claims (7)
1. application of the bimetallic catalyst in hydrogenolysis of glycerin prepares 1,3-PD, it is characterised in that：
The catalyst is with WOxIt is carrier, 2<x<3, active component is MoOx(2<x<3) and
Platinum；Wherein the content of Pt is the 0.01%-10%, MoO of catalyst weightxContent for catalysis
The 0.001%-10% of agent weight.
2. application according to claim 1, it is characterised in that：Its carrier WOxUsing solvent
Hot method is prepared, and detailed process is：
By 1-3 grams of WCl6It is dissolved in 100-200mL absolute ethyl alcohols, is transferred to after being completely dissolved
In water heating kettle, and in 12-600h is placed in 120-180 DEG C of baking oven, be cooled to room temperature suction filtration,
Washing, dry carrier WOx。
3. application according to claim 1 and 2, it is characterised in that：Prepared using infusion process
Bimetallic catalyst MoOx-Pt/WOxCatalyst, detailed process is：
1) WO is impregnated with platinum acid chloride solution firstxSupported carrier active component Pt, 40-140 DEG C
Under dry 4-36 hours after, in being reduced 0.5-10 hours at 100~600 DEG C of hydrogen atmosphere, obtain
Pt/WOx；
2) and then by Pt/WOxAdd in metamolybdic acid ammonium salt solution, 4~36 are dried at 40-140 DEG C
After hour, in being calcined at 100~600 DEG C and being reduced 0.5-10 hours, final catalyst is obtained
MoOx-Pt/WOx。
4. application according to claim 3, it is characterised in that：
Platinum acid chloride solution molar concentration 0.05-10M, metamolybdic acid ammonium salt solution molar concentration
0.05-10M。
5. application according to claim 3, it is characterised in that：Reduction temperature is preferably
300~400 DEG C.
6. application according to claim 1, it is characterised in that：The catalyst is used for glycerine
Hydrogenolysis is prepared in 1,3-PD reaction, and reaction raw materials are glycerite, and its mass concentration is
1-100%, Hydrogen Vapor Pressure is 0.1-20MPa, and reaction temperature is 10~500 DEG C.
7. application according to claim 6, it is characterised in that：Hydrogen Vapor Pressure is preferably
0.5~7MPa, reaction temperature is preferably 120~180 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108636440A (en) * | 2018-04-16 | 2018-10-12 | 江苏七洲绿色化工股份有限公司 | A kind of catalyst and preparation method thereof of glycerine water solution Hydrogenation 1,3- propylene glycol |
| CN111229204A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Application of bimetallic catalyst in preparation of 1, 5-pentanediol from tetrahydrofurfuryl alcohol |
| CN115709065A (en) * | 2022-11-23 | 2023-02-24 | 西安凯立新材料股份有限公司 | Catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003462A (en) * | 2007-01-25 | 2007-07-25 | 中国林业科学研究院林产化学工业研究所 | Method for preparing 1,3 propylene glycol by using glycerol method |
| CN102728380A (en) * | 2012-05-08 | 2012-10-17 | 中国科学院大连化学物理研究所 | Catalyst used for preparing 1,3-propylene glycol through glycerin hydrogenolysis, preparation method thereof, and application thereof |
| CN104582839A (en) * | 2012-08-30 | 2015-04-29 | 国立大学法人大阪大学 | Catalyst for hydrogenolysis of polyhydric alcohol and method for producing 1,3-propane diol by using the catalyst |
-
2015
- 2015-12-04 CN CN201510882004.1A patent/CN106824191B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003462A (en) * | 2007-01-25 | 2007-07-25 | 中国林业科学研究院林产化学工业研究所 | Method for preparing 1,3 propylene glycol by using glycerol method |
| CN102728380A (en) * | 2012-05-08 | 2012-10-17 | 中国科学院大连化学物理研究所 | Catalyst used for preparing 1,3-propylene glycol through glycerin hydrogenolysis, preparation method thereof, and application thereof |
| CN104582839A (en) * | 2012-08-30 | 2015-04-29 | 国立大学法人大阪大学 | Catalyst for hydrogenolysis of polyhydric alcohol and method for producing 1,3-propane diol by using the catalyst |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108636440A (en) * | 2018-04-16 | 2018-10-12 | 江苏七洲绿色化工股份有限公司 | A kind of catalyst and preparation method thereof of glycerine water solution Hydrogenation 1,3- propylene glycol |
| CN108636440B (en) * | 2018-04-16 | 2021-08-10 | 江苏七洲绿色化工股份有限公司 | Catalyst for preparing 1, 3-propylene glycol by hydrogenation of glycerol aqueous solution and preparation method thereof |
| CN111229204A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Application of bimetallic catalyst in preparation of 1, 5-pentanediol from tetrahydrofurfuryl alcohol |
| CN115709065A (en) * | 2022-11-23 | 2023-02-24 | 西安凯立新材料股份有限公司 | Catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation, and preparation method and application thereof |
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| CN106824191B (en) | 2019-05-14 |
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